Hair treatment composition, bleaching composition and hair color tone modifier composition

ABSTRACT

The present invention provides the following hair-treatment composition, bleaching composition and hair color tone modifier composition: 
     a hair-treatment composition containing: 
     (1) a ferrous salt, and 
     (2) a nonreducing organic chelate-forming compound capable of forming a chelate compound together with a ferrous ion, 
     and having a pH value of from 3 to 6, wherein the stability constant (K 1 ) between said ferrous ion and said nonreducing organic chelate-forming compound is lower than 3 and the ferrous salt, which is the chelate compound of said ferrous ion with said nonreducing organic chelate-forming compound, is highly soluble in water; 
     a hair-treatment composition containing: 
     (1) a ferrous salt, and 
     (2) a nonreducing organic chelate-forming compound represented by the following general formula (I): ##STR1## wherein R represents a straight-chain or branched hydrocarbon group having 1 to 10 carbon atoms or an oxane ring, and 
     m is an integer of from 1 to 6, capable of forming a chelate compound with a ferrous ion and having a pH value of from 3 to 6; 
     a bleaching composition consisting of either one of the above-mentioned hair-treatment compositions as the primary agent together with an aqueous composition containing 0.01 to 3% by weight of hydrogen peroxide and having a pH value of from 3 to 6 as the secondary agent; and 
     a hair color tone modifier composition obtained by adding a direct dye to the primary and/or secondary agents of the above-mentioned bleaching composition.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to pretreatment agents to be used beforebleaching or dyeing horny fibers such as the hair or idle hair, moreparticularly, a hair-treatment composition capable of supplying ferrousions in a stable state to the horny fibers under weakly acidic mildconditions; a bleaching composition whereby the horny fibers such as thehair or idle hair can be bleached without giving much damage theretounder weakly acidic mild conditions while scarcely irritating, forexample, the skin during the bleaching process; and a hair color tonemodifier composition (hair dyeing composition) obtained by adding a hairdye to said bleaching composition.

2. Description of the Prior Art

Known bleaching agents for horny fibers such as the hair or idle haircontain hydrogen peroxide as an essential factor of their constituents.In most cases, this hydrogen peroxide, including perborates andpercarbonates capable of liberating hydrogen peroxide at theapplication, would exert a bleaching effect in an aqueous state so as tooxidize and bleach melanin contained in the horny fibers such as thehair or idle hair. Such a bleaching agent is generally applied in theform of an alkaline aqueous solution (pH 8 to 11) in order to fullyachieve the bleaching effect of the hydrogen peroxide. However there isa problem that hydrogen peroxide contained in an alkaline aqueouscomposition is unstable, which makes it difficult to store such acomposition for a prolonged period of time.

Thus a bleaching agent containing hydrogen peroxide is frequentlysupplied in the form of a one-pack powdery bleaching agent, which is tobe dissolved so as to give an alkaline aqueous solution at theapplication, or a two-pack bleaching agent) wherein a powdery or aqueousalkaline agent composition is to be mixed with a water-soluble hydrogenperoxide composition immediately before the application. In order tofully achieve the bleaching effect of these powdery one-pack andtwo-pack bleaching agents, it is required to elevate the pH value withinan alkaline region or to increase the hydrogen peroxide content at theapplication. However these treatments, namely, the elevated pH value orincreased hydrogen peroxide content would irritate the skin and mucosaeso as to damage fibers including the hair.

Thus a pretreatment with ferrous ions has been conducted beforebleaching or dyeing horny fibers such as the hair or idle hair in orderto minimize the damage to the hair or improve the bleaching or dyeingeffect.

For example, U.S. Pat. No. 3,632,295 discloses a two-stage method forbleaching the hair comprising applying the primary agent containing aferrous salt to the hair and then applying an alkaline aqueous solutionof hydrogen peroxide (of pH 8 to 11) to the hair as the secondary agent;Japanese Patent Publication No. 37004/1987 discloses a three-packbleaching agent which consists of the primary agent containing asulfite, the secondary agent containing a ferrous salt and the tertiaryagent containing unstable hydrogen peroxide; and Japanese PatentPublication No. 55483/1986 discloses a two-pack hair dye consisting ofthe primary agent in the form of a commonly used hair tonic containing aferrous salt and the secondary agent which is in the form of a hairconditioner containing a color former and may be used at an appropriatestage thereafter.

Furthermore, West German Patent No. 3,149,978 discloses a methodcomprising applying a ferrous compound as a reducing agent together withphosphorous acid to keratin fibers and then bleaching the keratin fiberswith hydrogen peroxide.

An aqueous solution of a ferrous salt to be used as a pretreatment agentsuffers from some troubles such that it would form hardly solubleferrous hydroxide at a pH value of 5 or higher and that it wouldirritate the skin or mucosae at a pH value of 3.0 or lower. In order tostably and safely penetrate a ferrous salt into the hair, therefore, ithas been attempted to control the pH value by using an ferrous saltsolution as a buffer system. However there are still some problems inthis method. Among organic acids commonly used in a buffer system,acetic acid has a characteristic odor while citric acid would cause thecoloration of a chelate compound thereof with the ferrous ion.

When an alkaline aqueous solution of hydrogen peroxide is to be used asa bleaching agent, as in the case of the above-mentioned method of theU.S. Pat. No. 3,632,295, the hydrogen peroxide in said alkaline aqueoussolution of hydrogen peroxide is unstable. Thus it is difficult toprovide a stable aqueous composition available in practice unless theproduct is formulated into a three-pack composition wherein an alkalicomposition (the secondary agent) is mixed with a water-soluble hydrogenperoxide composition (the tertiary agent) immediately before theapplication.

On the other hand, the above-mentioned three-pack bleaching agent of theJapanese Patent Publication no. 37004/1987 cannot always be convenient,since it requires a complicated bleaching procedure and a long treatmentperiod.

In the case of the above-mentioned bleaching method described in theWest German Patent No. 3,149,978, furthermore, sufficient care should betaken in the pretreatment conducted under strongly acidic conditions andin the rinsing with an acidic solution such as phosphoric acid forremoving the remaining phosphorous acid. Further, this product wouldsometimes cause significant irritation on the skin and mucosae whenapplied to the body.

When a hydrogen peroxide solution alone is to be used within a weaklyacidic or neutral region, a satisfactory bleaching effect can bescarcely achieved. When the hydrogen peroxide concentration is increasedor the solution is repeatedly used in order to enhance the bleachingeffect, fibers including the hair would be frequently damaged.

SUMMARY OF THE INVENTION

It is a first object of the present invention to provide ahair-treatment composition stably containing ferrous ions which wouldscarcely irritate the skin or mucosae.

It is a second object of the present invention to provide an aqueousbleaching composition, which has high safety to the skin and mucosae,exerts a bleaching effect superior to those of known alkalihydrogenperoxide bleaching agents and can be easily handled, as well as a haircolor tone modifier composition (hair dyeing composition) whereby thecolor tone of the hair can be modified.

The present inventors have conducted extensive studies and thus found ahair-treatment composition which can stabilize ferrous ions within a pHrange safe to the skin and mucosae while scarcely damaging the hair,suppress the formation of hardly soluble ferrous hydroxide andeffectively and rapidly penetrate the ferrous ions into the hair such acomposition can achieve the first object of the present invention andcan be obtained by adding a specific compound to a hair-treatmentcomposition so as to form a chelate compound of said compound withferrous ions.

The present inventors have further conducted studies on the convenience,storage stability and reduction of irritation of bleaching agents. As aresult, they have found out that the second object of the presentinvention can be achieved by formulating a two-pack compositionconsisting of the above-mentioned hair-treatment composition as theprimary agent and an aqueous composition, which contains hydrogenperoxide at a specific concentration and has a pH value adjusted withina specific range, as the secondary agent.

The present invention has been completed based on these findings.Accordingly, the invention provides for a hair-treatment compositioncomprising:

(1) a ferrous salt, and

(2) a nonreducing organic chelate-forming compound capable of forming achelate compound with a ferrous ion,

and having a pH value of from 3 to 6, wherein the stability constant(K₁) between said ferrous ion and said nonreducing organicchelate-forming compound is lower than 3 and the ferrous salt, which isthe chelate compound of said ferrous ion with said nonreducing organicchelate-forming compound, is highly soluble in water. Thishair-treatment composition will be called the first hair-treatmentcomposition hereinafter.

Furthermore, the present invention provides another hair-treatmentcomposition comprising:

(1) a ferrous salt, and

(2) a nonreducing organic chelate-forming compound represented by thefollowing general formula(I): ##STR2## wherein R represents a straightchain or branched hydrocarbon group having 1 to 10 carbon atoms or anoxane ring, and

m is an integer of from 1 to 6,

capable of forming a chelate compound with a ferrous ion and having a pHvalue of from 3 to 6. This hair-treatment composition will be called thesecond hair-treatment composition hereinafter. In the above generalformula (I), the hydroxyl group may be bound at any position to thehydrocarbon group R.

The present invention furthermore provides a bleaching composition whichconsists of the above-mentioned first or second hair-treatmentcomposition as the primary agent and an aqueous composition containing0.01 to 3% by weight of hydrogen peroxide and having a pH value of from3 to 6 as the secondary agent.

The present invention furthermore provides a hair color tone modifiercomposition obtained by adding a direct dye to the above-mentionedprimary agent and/or the secondary agent of the above-mentionedbleaching composition.

The first and second hair-treatment compositions of the presentinvention, in which ferrous ions are stably blended, can supply theferrous ions in a stable state to the horny fibers. Thus the hair can beexcellently bleached or dyed without being damaged. Further thesecompositions are adjusted to a pH value of from 3 to 6 and thus scarcelyirritate the skin or mucosae.

Further, the bleaching composition of the present invention is highlysafe to the skin and mucosae and exerts a bleaching effect superior tothose of known alkali-hydrogen peroxide bleaching agents. In addition,it can be readily handled while scarcely damaging the hair.

Furthermore, the hair color tone modifier composition of the presentinvention is highly safe to the skin and mucosae and can be easilyhandled so as to widely modify the color tone of the hair. [Function]

The first or second hair-treatment composition of the present inventionmay be used in the following manner. First, said composition is appliedto horny fibers such as the hair and then slightly rinsed. Thus theferrous salt is penetrated into the hair which prevents the hair frombeing damaged in the subsequent bleaching or dyeing step. In addition,the bleaching and dyeing can be excellently conducted.

The bleaching composition of the present invention may be used afollows. First, horny fibers such as the hair are treated with theprimary agent and weakly rinsed. Next, the secondary agent is applied tothe hair, which is allowed to dry as such or dried by heating with, forexample, a blower. Thus the hair is bleached. Alternately, the secondaryagent may be washed away after the completion of the bleaching, ifdesired.

The hair color tone modifier composition of the present invention may beused in the following manner. First, the hair is treated with theprimary agent and weakly rinsed. Next, the secondary agent is applied assuch to the hair, which is allowed to dry as such or dried by heatingwith, for example, a blower. Thus the color tone of the hair can bemodified and dyeing can be excellently conducted.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 and 2 are each a graph showing a relationship between thelightening effect observed in the bleached hair and the content ofcysteic acid.

DETAILED DESCRIPTION OF THE INVENTION

The first hair-treatment composition of the present invention is anaqueous composition containing a ferrous salt and having a pH valueadjusted to from 3 to 6.

Examples of the ferrous salt include ferrous acetate, ferrous nitrate,ferrous sulfate and ferrous chloride. Among these compounds, ferroussulfate and ferrous chloride are preferable from the viewpoints of, forexample, odor. The ferrous salt may be preferably contained in the firsthair-treatment composition of the present invention in an amount of from0.01 to 10% by weight.

When the pH value of said hair-treatment composition is adjusted withinthe range as specified above, said composition becomes safe to the skinand mucosae during treatment of the hair. Further, it scarcely damagesfibers and the ferrous ions of the ferrous salt can be readilyincorporated into the hair to form a complex with melanin. The pH valueof the first hair-treatment composition of the present invention may beadjusted to from 3 to 6 by using a commonly employed acid such ashydrochloric or sulfuric acid or a common alkaline aqueous solution suchas a sodium hydroxide or potassium hydroxide aqueous solution.

The first hair-treatment composition of the present invention furthercontains a nonreducing organic chelate-forming compound capable offorming a chelate compound with a ferrous ion. The stability constant[K₁ ; refer to Chaberek; "Organic Sequestering Agents", published byJohn Wiley (1959)] between said ferrous ion and said nonreducing organicchelate-forming compound should be lower than 3 and a ferrous salt,which is the chelate compound of the above-mentioned ferrous ion and theabove-mentioned nonreducing organic chelate-forming compound, should behighly soluble in water. The expression "highly soluble in water" asused herein means that the solubility of said ferrous salt in purifiedwater at 20° C. is 0.1% by weight or more.

When the stability constant (K₁) of the ferrous salt, namely, theabove-mentioned chelate compound is adjusted to lower than 3, theferrous salt can be more stably blended and stored in the form of anaqueous solution. The above-mentioned nonreducing organicchelate-forming compound is a compound which forms a chelate compoundwith a ferrous ion, suppresses the formation of a hydroxo complex ofsaid ferrous ion, which is insoluble and forms a precipitate, andpromotes the effective and rapid penetration of the ferrous ion into thehair. As the nonreducing organic chelate-forming compound, thoserepresented by the following general formula (II) are preferable:##STR3##

In the above general formula (II), R¹ wherein R² may be either the sameor different from each other and R¹ preferably represents a hydrogenatom, a straight-chain or branched alkyl group having one to five carbonatoms or an alkenyl group having one to five carbon atoms, R² whereinpreferably represents a straight-chain or branched alkyl group havingone to five carbon atoms or an alkenyl group having one to five carbonatoms, n is preferably from 0 to 2 and m is preferably from 0 to 6.Examples of such a nonreducing organic chelate-forming compound includeorganic acids such as lactic acid, glycolic acid, hydroxybutyric acid,glyceric acid, β-hydroxyglutaric acid, gluconic acid and glucuronicacid. By taking the odor into consideration, it is still preferable touse a hydroxy carboxylic acid such as lactic acid or glycolic acid. Itis undesirable to use commonly employed organic chelate-formingcompounds, for example, citric acid, or its salts, orethylenediaminetetraacetic acid or its salts, since each of thesecompounds has a stability constant (K₁) with a ferrous ion exceeding 3and the formation of a complex of said compound with a ferrous ion wouldlower the oxidation potential of the complex. When the composition thusobtained is stored, in particular at a high temperature, therefore, thecomplex would be partially oxidized by the contact thereof with thedissolved oxygen in the composition or with the atmosphere, which wouldfrequently cause coloration and the formation of a Fe³⁺ complex.

Furthermore, succinic acid, malic acid and tartaric acid would each forma complex salt with a ferrous ion. Although this complex salt has astability constant (K₁) lower than 3, it has only a low solubility inwater and thus can be hardly obtained in the form of a stable aqueouscomposition. Thus it is also undesirable to use there acids.

The above-mentioned nonreducing organic chelate-forming compound may bepreferably contained in the first hair-treatment composition of thepresent invention in an amount of 0.1 to 10.0% by weight.

A nonreducing organic chelate-forming compound, which has a stabilityconstant (K₁) lower than 3 and forms a chelate compound (i.e., a ferroussalt) highly soluble in water, can be used together with an organicreducing agent such as ascorbic acid.

Now the second hair-treatment composition of the present invention willbe described in detail.

Similar to the above-mentioned first hair-treatment composition, thesecond hair-treatment composition of the present invention is an aqueouscomposition containing a ferrous salt and having a pH value adjusted tofrom 3 to 6.

As said ferrous salt, those described with respect to theabove-mentioned first hair-treatment composition may be used. Similar tothe case of the above-mentioned first hair-treatment composition, theferrous salt may be preferably contained in the composition in an amountof from 0.01 to 10% by weight.

The pH value of the second hair-treatment composition of the presentinvention may be adjusted in the same manner as the one employed in thecase of the above-mentioned first hair-treatment composition.

As the nonreducing organic chelate-forming compound of theabove-mentioned general formula (I) to be used in the secondhair-treatment composition of the present invention, lactic acid,glycolic acid, hydroxybutyric acid, glyceric acid, gluconic acid andglucuronic acid may be used. By taking the odor into consideration, itis still preferable to use lactic acid or glycolic acid. Thisnonreducing organic chelate-forming compound (I) may be preferablycontained in the second hair-treatment composition of the presentinvention in an amount of from 0.1 to 10.0% by weight. The secondhair-treatment composition of the present invention may further containan organic reducing agent such as ascorbic acid as anotherchelate-forming compound.

It is preferable to add a cationic polymer and/or a cationic surfactantto the above-mentioned first and second hair-treatment compositions ofthe present invention to thereby improve the texture of the hair. Inorder to further improve this conditioning effect, these compositionsmay be formulated into an emulsion by optionally adding appropriateadditive(s) such as a higher alcohol thereto.

Furthermore, the above-mentioned first and second hair-treatmentcompositions of the present invention may be processed into variousforms, for example, rinse, treatment or preshampoo treatment. Thusvarious additives commonly used in the production of these products, forexample, UV absorbers, cationic surfactants, nonionic surfactants,wetting agents, thickners such as water-soluble polymers, pearlescentpigments such as glycol esters, antidandruff agents, medical ingredientssuch as vitamins, preservatives such as paraben, hair-setting polymerssuch as acrylic acid resin solutions, various perfumes and colorants maybe added thereto, so long as the effects of the present invention arenot deteriorated thereby.

In order to maintain the first and second hair-treatment compositions ofthe present invention in a stable state for a prolonged period of time,it is preferable to shut off these compositions from contact withexternal air. Therefore they may be preferably filled in hermeticallysealed containers such as a laminate tube or an aerosol container.Examples of these containers include a double-wall aerosol container ofa piston can type filled with a liquefied gas, for example, carbondioxide, nitrogen, nitrous oxide, Freon, LPG or a mixture thereof, anonaerosol double-well container of a piston can type, a batting can andan Excel System (mfd. by Container Industries Inc.) where a container isdirectly pressurized with a rubber so as to extrude its contents, whichare substitutes for the above-mentioned piston cans, a laminate tubemade of a gas-impermeable material and a unit-dose package.

The first and second hair-treatment compositions of the presentinvention may be used in, for example, the following manner.

The first or second hair-treatment composition of the present inventionis applied to the hair of the body to be treated allowed to stand for awhile, and weakly rinsed. This procedure is repeated so as to penetratethe ferrous salt into the hair. This treatment enhances the bleachingeffect and prevent the hair from being damaged in the subsequentbleaching step with the use of hydrogen peroxide. When the hair issubsequently dyed with a dye composition containing a colorant such astannic acid or gallic acid, alternately, the color would be developed bythe reaction with iron which has been penetrated by the pretreatmentwith the first or second hair-treatment composition of the presentinvention. Thus the hair can be excellently dyed.

Now the bleaching composition of the present invention will be describedin detail.

The bleaching composition of the present invention consists of the abovementioned first or second hair-treatment composition as the primaryagent together with an aqueous composition containing hydrogen peroxideas the secondary agent.

The above-mentioned secondary agent in the bleaching composition of thepresent invention is an aqueous composition which is employed as ableaching agent after treating the hair with the above-mentioned primaryagent. The secondary agent contains hydrogen peroxide at a concentrationof from 0.01 to 3% by weight and has a pH value adjusted to from 3 to 6.When the hydrogen peroxide concentration exceeds 3%, the hair might bedamaged. When the pH value falls within the range as specified above,the composition can exert an excellent bleaching effect while loweringthe damage to the hair and the irritation on the skin and mucosae in thetreatment with the secondary agent. The pH value of this secondary agentcan be adjusted in the same manner as that employed in adjusting the pHvalue of the above-mentioned first or second hair-treatment composition,namely, the primary agent.

The secondary agent can further contain a chelating agent, for example,EDTA, an oxyquinoline salt or acetanilide so as to stabilize thehydrogen peroxide.

When this bleaching composition is to be applied to the hair, theabove-mentioned secondary agent may contain a polymer stable in thehydrogen peroxide system, for example, a specific ester type polymerhaving the following structural formula as a styling agent. ##STR4##

The above-mentioned ester polymer can impart a stable hair stylingeffect to the secondary agent containing hydrogen peroxide. Thus thesecondary agent can be applied not only to a preparation to be usedexclusively for bleaching but also to a commonly available hair stylingagent which also exerts a bleaching effect and can be repeatedly usedeveryday, as will be shown hereinafter.

Thus the bleaching composition of the present invention, which scarcelydamages horny fibers, can be widely used as, for example, a pretreatmentagent to be used prior to bleaching or dyeing the fibers. Since itscarcely irritates the skin and mucosae, it is particularly suitable fortreating idle hair and the hair.

Further, the primary agent of the bleaching composition of the presentinvention can be emulsified so as to give an aqueous gel, a cream or anemulsion. Furthermore, it can be formulated into a mousse by blendingwith a propellant. On the other hand, the secondary agent of thebleaching composition of the present invention may be used in the formof an aqueous liquid or a gel. Thus it can be applied to the hair assuch. Alternately, it may be filled in a spray container or an aerosolcontainer and sprayed at the time of use.

Now the hair color tone modifier composition (hair dyeing composition)of the present invention will be described in detail.

The hair color tone modifier composition of the present invention, whichis obtained by applying the above-mentioned bleaching composition, isprepared by adding a direct dye to the above-mentioned primary and/orsecondary agent of the bleaching composition. The addition of the dye tothe primary and/or secondary agent of the bleaching composition makes itpossible to bleach and lighten the inherent color of the hair as well asto dye the hair with the direct dye to thereby give a desired colorduring the bleaching stage. In addition, it is highly safe to the skinand mucosae and scarcely damages the hair. Therefore, the hair colortone modifier composition of the present invention can modify the colortone of the hair over a wide range of dark colors, including dark blond,dark brown and black, compared with a conventional hair color tonemodifier composition which contains not an oxidation dye but a directdye alone and exclusively depends on the dyeing effect of said dye.

Examples of the direct dye to be used in the hair color tone modifiercomposition of the present invention include basic direct dyes, acidicdirect dyes, disperse dyes and nitro dyes. It is particularly preferableto use a basic dye such as an allyanol basic dye, a disperse dye, anitro dye or a mixture thereof as the direct dye to be added to thesecondary agent, since such a dye should be stable to the oxidizingagent.

When the above-mentioned direct dye is to be added to the primary agentof the bleaching composition alone, it may be preferably contained inthe primary agent in an amount of from 0.0001 to 5% by weight. When itis to be added to the secondary agent of the bleaching compositionalone, it may be preferably contained in the secondary agent in anamount of from 0.0001 to 5% by weight. When it is to be added to both ofthe primary and secondary agents, it may be preferably contained in theprimary agent in an amount of from 0.0001 to 5% by weight and in thesecondary agent in an amount of from 0.0001 to 5% by weight.

To further illustrate the present invention, and not by way oflimitation, the following Examples will be given.

EXAMPLE 1: Stability test on hair-treatment composition

Hair-treatment compositions of formulations specified in the followingTable 1 (invention products 1 and 2 and comparative products 1 to 7)were prepared. Then the stability of each product to a ferrous salt wastested. The stability was evaluated by determining the solubility of theferrous salt when added to each product and observing the coloration ofeach product when stored at 40° C. for 20 days. Table 1 summarizes theresults. When the ferrous salt is not dissolved but forms a precipitateupon addition, no coloration was examined any more.

                                      TABLE 1                                     __________________________________________________________________________    Formulation                                                                              Invention product                                                                         Comparative product                                    (% by wt.) 1     2     1     2    3     4     5     6     7                   __________________________________________________________________________    ferrous sulfate (7H.sub.2 O)                                                              0.98  0.98 0.98   0.98                                                                               0.98  0.98  0.98  0.98 0.98                lactic acid                                                                              4.5   4.5   --    --   --    --    --    --    --                  glycolic acid                                                                            --    3.8   --    --   --    --    --    --    --                  ethylenediamine-                                                                         --    --    1.46  --   --    --    --    --    --                  tetraacetic acid                                                              citric acid                                                                              --    --    --    9.6  --    --    --    --    --                  succinic acid                                                                            --    --    --    --   5.9   --    --    --    --                  tartaric acid                                                                            --    --    --    --   --    7.5   --    --    --                  sodium bisulfite                                                                         --    --    --    --   --    --    5.2   --    --                  phosphoric acid                                                                          --    --    --    --   --    --    --    4.9   --                  ascorbic acid                                                                             0.40  0.40 0.40   0.40                                                                               0.40  0.40  0.40  0.40 0.40                sodium hydroxide                                                                         q.s.  q.s.  q.s.  q.s. q.s.  q.s.  q.s.  q.s.  --                  hydrochloric acid                                                                        --    --    --    --   --    --    --    --    q.s.                xanthan gum                                                                              0.3   0.3   0.3   0.3  0.3   0.3   0.3   0.3   0.3                 purified water                                                                           balance                                                                             balance                                                                             balance                                                                             balance                                                                            balance                                                                             balance                                                                             balance                                                                             balance                                                                             balance             pH         3.6   3.6   3.6   3.6  3.6   3.6   3.6   3.6   1.5                 Stability                                                                     coloration no change                                                                           no change                                                                           change into                                                                         browning                                                                           --*   --*   --*   --*   no                                         orange or                          change                                     brown                                                  solubility soluble                                                                             soluble                                                                             soluble                                                                             soluble                                                                            precipitated                                                                        precipitated                                                                        precipitated                                                                        precipitated                                                                        soluble             __________________________________________________________________________     *Coloration was not tested since a precipitate was formed immediately         after the addition.                                                      

As Table 1 shows, the ferrous salt was stably contained in eachhair-treatment composition of the invention.

EXAMPLE 2: Skin irritation test of hair-treatment composition

The irritating effects on the skin of the invention products 1 and 2 andthe comparative product 7, each obtained in Example 1, were evaluated inthe following manner. A closed patch test was conducted with the use ofGuinea pigs (N=4 or 5) for 24 hours. 48 hours thereafter, the conditionsof the animals were observed with the naked eye and evaluated accordingto the following criteria. Table 2 gives the results.

Criteria:

0: no change,

1: slight erythema, and

2: significant erythema.

                  TABLE 2                                                         ______________________________________                                                 Invention                                                                              Invention Comparative                                                product 1                                                                              product 2 product 7                                         ______________________________________                                        Skin irritation                                                                          0          0         1.0                                           score                                                                         ______________________________________                                    

As Table 2 shows, each invention product showed no skin irritation.

EXAMPLE 3: Application test of hair-treatment Composition

Hair-treatment compositions of the formulations specified in thefollowing Table 3 (the invention products 3 to 5) were prepared.

                  TABLE 3                                                         ______________________________________                                                      Invention product                                                             3      4          5                                             ______________________________________                                        Formulation                                                                   (% by wt.)                                                                    ferrous sulfate (7H.sub.2 O)                                                                   0.98     0.98       0.98                                     ascorbic acid   0.6      0.6        0.6                                       lactic acid     4.5      4.5        4.5                                       cationized      --       0.5        0.5                                       cellulose.sup.1                                                               cationic surfactant.sup.2                                                                     5.4      1.1        --                                        cationic surfactant.sup.3                                                                     2.0      --         --                                        nonionic surfactant.sup.4                                                                     --       0.5        0.5                                       nonionic surfactant.sup.5                                                                     1.0      --         --                                        behenyl alcohol 2.0      --         --                                        propylene glycol                                                                              10.0     4.0        4.0                                       perfume         0.2      0.2        0.2                                       methylparaben   0.3      0.3        0.3                                       xanthan gum     0.3      0.3        0.3                                       sodium hydroxide                                                                              q.s.     q.s.       q.s.                                      purified water  balance  balance    balance                                   pH of composition                                                                             3.8      3.8        3.8                                       Form of composition                                                                           creamy   trans-     trans-                                                             parent     parent                                    ______________________________________                                         Note:                                                                         .sup.1 Polymer JR (mfd. by Union Carbide Corp.)                               .sup.2 Stearyltrimethylammonium chloride (30% aqueous solution).              .sup.3 Dimethyldialkylammonium chloride [branched quaternary ammonium sal     derived from commercially available oxosynthesis alcohol having 12 to 15      carbon atoms (equivalent mixture of Dobanol 23 with Dobanol 25 mfd. by        Mitsubishi Petrochemical Co., Ltd.), degreed of branching: 20%].              .sup. 4 Ethylene oxide adduct of a synthetic secondary alcohol having 11      to 15 carbon atoms (average number of added ethylene oxide molecules: ca.     9).                                                                           .sup.5 Polyoxyethylene 2octyldodecyl ether (average number of added           etylene oxide molecules: ca. 20).                                        

Further, a hair-dyeing cream of the following formulation was prepared.

    ______________________________________                                        Formulation of hair-dyeing cream                                                                        % by wt.                                            ______________________________________                                         (1)   self-emulsifiable glyceryl monostearate                                                              4.5                                              (2)   ethylene glycol monostearate                                                                         3.5                                              (3)   polyoxyethylene sorbitan tristearate                                                                 1.0                                              (4)   paraffin wax           3.0                                              (5)   liquid paraffin        25.0                                             (6)   vaseline               5.0                                              (7)   ceresin wax            2.0                                              (8)   isopropyl myristate    4.5                                              (9)   sodium cetyl sulfate   1.5                                             (10)   gallic acid            1.0                                             (11)   ferrous sulfate        1.0                                             (12)   ascorbic acid          0.2                                             (13)   citric acid            0.2                                             (14)   ethylene carbonate     10.0                                            (15)   water                  37.1                                            (16)   perfume                0.5                                                    total                  100.0                                           ______________________________________                                    

Preparation of Hair-dyeing Cream

The above-mentioned components (9), (10) and (13) were homogeneouslydissolved in a portion of the purified water at approximately 80° C. Theabove components (1) to (8) were made molten by heating to approximately90° C. and then added to the mixture solution obtained above understirring. The resulting mixture was homogeneously stirred and cooled.The above-mentioned components (11) and (12) were homogeneouslydissolved in the rest of the water and then added together with thecomponent (14) to the mixture obtained above at 50° C. After mixing andcooling, the mixture was filled in an Excel bottle to thereby give acreamy hair-dye (hair-dyeing cream).

Dyeing

The effect of the invention product given in Table 3 was examined in thefollowing manner. An appropriate amount of said invention product givenin Table 3 (a conditioning composition) was applied to gray hair aftershampooing and allowed to stand for several minutes. Then it was rinsedaway and the hair was further treated with the above-mentionedhair-dyeing cream. This procedure was repeated. Thus, the white hairslowly turned black under very excellent conditions.

EXAMPLE 4: Application test of hair-treatment composition

A hair-dyeing lotion of the following formulation was prepared by thefollowing method.

    ______________________________________                                        Formulation           % by wt.                                                ______________________________________                                        (1)    solid logwood extract                                                                            2.0                                                        (hematoxylin content: ca. 50%)                                         (2)    glucose            1.0                                                 (3)    perfume            0.5                                                 (4)    purified water     96.5                                                       total              100.00                                              ______________________________________                                    

Preparation of Hair-dyeing Lotion

The above-mentioned component (1) was dissolved in component (4) understirring. Next, components (2) and (3) were added thereto and stirringto thereby give a transparent aqueous solution (a hair-dyeing lotion).

Dyeing

Another effect of the product obtained in the above-mentioned Example 3was examined in the following manner. An appropriate amount of theinvention product given in Table 3 (conditioning composition) wasapplied to white hair after shampooing. Then it was allowed to stand forseveral minutes and rinsed away. Next, an appropriate amount of theabove-mentioned hair-dyeing lotion was applied to the white hair. Afterbeing allowed to stand for several minutes, it was rinsed away. Thisprocedure was repeated. Thus, the white hair slowly turned black undervery excellent conditions.

EXAMPLE 5: Bleaching test of a bleaching composition

In this Example, invention products 6 to 11, each consisting of theprimary and secondary agents listed in Table 4, were prepared andsubjected to the following test.

Undamaged black hair of a German was used as the test hair. Samples eachweighing 1 g were taken from the test hair and treated with each primaryagent specified in Table 4 at 55° C. for 60 minutes. Next, the hairsample was washed with warm water for one minute and the excess moisturewas removed. Then it was treated with the corresponding secondary agentspecified in Table 4 at 55° C. for 60 minutes. The change in the colortone of the above-mentioned black hair thus treated with the primary andsecondary agents was measured. The change in the color tone wasdetermined by measuring the lightness (L) in the Hunter color differencemeter and expressed by the change in the lightness (ΔL) which isemployed as a measure. Table 4 gives the results. The damage to the haircaused by the above-mentioned bleaching procedure was examined by usingthe content of cysteic acid formed by the treatment as a measure.Namely, the bleached hair was hydrolyzed and the content (% by mol) ofthe cysteic acid determined with an amino acid analyzer was compared.Table 4 gives the results.

The irritation on the skin was evaluated in the following manner. Eachof the primary and secondary agents was subjected to a closed patch testfor 24 hours with the use of Guinea gigs (N=4 or 5). 48 hoursthereafter, the average scores were compared with each other.

    -:0,±:1,+:2, and ++:3.

In a comparative case, an aqueous solution of hydrogen peroxide wasmixed with an alkali solution immediately before the use to therebyprepare the secondary agent (cf. Table 4), which was then applied to thehair so as to examine the effect of a conventional alkaline bleachingagent.

The results given in Table 4 suggest the following facts:

(1) The invention products 6 to 11 each showed a large change in L (ΔL),which gave a remarkable lightening (bleaching) effect as compared withthe comparative product 8.

(2) The invention products 6 to 11 each had a low cysteic acid content,when gave slight damage to the hair as compared with the comparativeproduct 8. Furthermore, the invention products 6 to 11 each gave aslight irritating effect on the skin as compared with the comparativeproduct 8.

                                      TABLE 4                                     __________________________________________________________________________                  Invention product                         Comparative           Composition (%)                                                                             6      7      8      9      10     11     product               __________________________________________________________________________                                                            8                     Primary agent                                                                 ferrous sulfate (7H.sub.2 O)                                                                 0.98   0.98   0.98   0.98   0.98   0.98  --                    ascorbic acid 0.6    0.6    0.6    0.6    0.6    0.6    --                    lactic acid   4.5    4.5    4.5    4.5    4.5    4.5    --                    sodium hydroxide                                                                            q.s.   q.s.   q.s.   q.s.   q.s.   q.s.   --                    xanthan gum   0.3    0.3    0.3    0.3    0.3    0.3    --                    purified water                                                                              balance                                                                              balance                                                                              balance                                                                              balance                                                                              balance                                                                              balance                                                                              --                    pH            5.0    5.0    5.0    5.0    3.0    6.0    --                    Secondary agent                                                               hydrogen peroxide (30%)                                                                     6.6    6.6    6.6    6.6    6.6    6.6    6.6                   acetic acid   7.2    7.2    7.2    7.2    7.2    7.2    --                    acetanilide    0.02   0.02   0.02   0.02   0.02   0.02   0.02                 oxyquinoline   0.01   0.01   0.01   0.01   0.01   0.01   0.01                 sodium hydroxide                                                                            q.s.   q.s.   q.s.   q.s.   q.s.   q.s.   q.s.                  aqueous ammonia (28%)                                                                       --     --     --     --     --     --     3.1                   purified water                                                                              balance                                                                              balance                                                                              balance                                                                              balance                                                                              balance                                                                              balance                                                                              balance               pH            3.0    4.0    5.0    6.0    4.0    4.0    10.4                  Lightening effect (ΔL)                                                                15.8   14.3   15.1   16.8   13.8   12.1   7.3                   (hair color tone)                                                                           (dark blond)                                                                         (dark blond)                                                                         (dark blond)                                                                         (dark blond)                                                                         (dark blond)                                                                         (dark blond)                                                                         (dark brown)          Cysteic acid content (% by                                                                   1.11   1.33   0.89   1.12   1.25   1.67  2.1                   mol)                                                                          Skin irritation score                                                         Primary agent 0      0      0      0      0.2    0      --                    Secondary agent                                                                             1.4     1.25  1.0    1.0     1.25   1.25  2.6                   __________________________________________________________________________

EXAMPLE 6: Bleaching test of bleaching composition

In this Example, invention products 12 to 14 each consisting of theprimary and secondary agents listed in the following Table 5 wereprepared and subjected to the following bleaching test.

Similar to Example 5, samples, each weighing 1 g, of undamaged blackhair of a German were prepared and treated with each primary agentlisted in Table 5 at 55° C. for 60 minutes. Next, it was rinsed and theexcess moisture was removed. Then the corresponding secondary agentlisted in Table 5 was applied to the hair sample thus treated and driedby allowing it to stand overnight, as in the case of the application ofa conventional set lotion. Subsequently, this treatment with thesecondary agent was repeated everyday. Thus the treatment with thesecondary agent was conducted ten times in total. In a comparative case,a hair sample was treated with the secondary agent of the comparativeproduct 9 (listed in Table 5) in the same manner as the one describedabove. The results are given in Table 5 and FIG. 1.

The results given in Table 5 and FIG. 1 indicate that the inventionproducts 12 to 14 each gave slight damage to the formation of cysteicacid, when compared with the comparative product 9 at the pointproviding for the same bleaching effect.

                  TABLE 5                                                         ______________________________________                                                                    Comp-                                                        Invention product                                                                              arative                                           Composition (%)                                                                            12       13       14     product 9                               ______________________________________                                        Primary agent                                                                 ferrous sulfate (7H.sub.2 O)                                                                0.027    0.27     2.70  --                                      ascorbic acid                                                                              0.6      0.6      0.6    --                                      lactic acid  4.5      4.5      4.5    --                                      sodium hydroxide                                                                           q.s.     q.s.     q.s.   --                                      xanthan gum  0.3      0.3      0.3    --                                      water        balance  balance  balance                                                                              --                                      pH           3.6      3.6      3.6    --                                      Secondary agent                                                               hydrogen peroxide                                                                          1.0      1.0      1.0    1.0                                     (30%)                                                                         acetic acid  7.2      7.2      7.2    7.2                                     acetanilide   0.02     0.02     0.02   0.02                                   oxyquinoline  0.01     0.01     0.01   0.01                                   sodium hydroxide                                                                           q.s.     q.s.     q.s.   q.s.                                    water        balance  balance  balance                                                                              balance                                 pH           3.6      3.6      3.6    3.6                                     Skin irritation score                                                         Primary agent                                                                              0.2      0        0      --                                      Secondary agent                                                                            0.2      0.2      0.2    0.2                                     ______________________________________                                    

EXAMPLE 7

In this Example, invention products 15 to 17 consisting of the primaryand secondary agents listed in the following 6 were prepared andsubjected to the following bleaching test.

Similar to Example 6, 1 g of undamaged black hair of a German wastreated each with a primary agent listed in Table 6 at 35° C. for fiveminutes. Next, it was rinsed and the excess moisture was removed. Thenthe corresponding secondary agent listed in Table 6 was applied to thehair and dried by allowing it to stand overnight, as in the case of theapplication of a conventional set lotion. The procedure was repeated tentimes in total everyday with the use of the primary agent together withthe secondary agent. In the cases of the comparative products 10 to 12,the secondary agent listed in Table 6 was used alone in the treatment.Table 6 gives the results.

The results given in Table 6 and FIG. 2 indicate that the inventionproducts 15 to 17 each gave slight damage to the hair, when comparedwith the comparative products 10 to 12 at the point providing for thesame bleaching effect.

                                      TABLE 6                                     __________________________________________________________________________                 Invention product                                                                            Comparative product                               Composition (%)                                                                            15   16   17   10   11   12                                      __________________________________________________________________________    Primary agent                                                                 ferrous sulfate (7H.sub.2 O)                                                                0.98                                                                               0.98                                                                               0.98                                                                              --   --   --                                      ascorbic acid                                                                              0.6  0.6  0.6  --   --   --                                      lactic acid  4.5  4.5  4.5  --   --   --                                      sodium hydroxide                                                                           q.s. q.s. q.s. --   --   --                                      xanthan gum  0.3  0.3  0.3  --   --   --                                      purified water                                                                             balance                                                                            balance                                                                            balance                                                                            --   --   --                                      pH           3.6  3.6  3.6  --   --   --                                      Secondary agent                                                               hydrogen peroxide (30%)                                                                    1.7  3.3  9.9  1.7  3.3  9.9                                     acetanilide   0.02                                                                               0.02                                                                               0.02                                                                               0.02                                                                               0.02                                                                               0.02                                   oxyquinoline  0.01                                                                               0.01                                                                               0.01                                                                               0.01                                                                               0.01                                                                               0.01                                   75% phosphoric acid                                                                        q.s. q.s. q.s. q.s. q.s. q.s.                                    purified water                                                                             balance                                                                            balance                                                                            balance                                                                            balance                                                                            balance                                                                            balance                                 pH           3.6  3.6  3.6  3.6  3.6  3.6                                     Skin irritation score                                                         Primary agent                                                                              0.2  0.2  0.2  --   --   --                                      Secondary agent                                                                             1.25                                                                              1.4  1.8  1.4  1.4  1.8                                     __________________________________________________________________________

EXAMPLE 8: Conditioning effect of hair-treatment composition

In this Example, the conditioning effects of the invention products 3 to5 obtained in Example 3 and a comparative product 13 of the formulationas specified in the following Table 7 were tested.

The invention products 3 to 5 and the comparative product 13 wereapplied to the hair. Then the touch of the hair at the application andthat after drying were organoleptically evaluated to determine theconditioning effect of each product. Table 7 gives the results.

As Table 7 indicates, the invention products 3 to 5 showed each anexcellent conditioning effect, while the comparative product 13 wasinferior to them in conditioning effect.

                                      TABLE 7                                     __________________________________________________________________________                 Invention product                                                                              Comparative                                                  3    4     5     product 13                                      __________________________________________________________________________    Formulation (% by wt.)                                                        ferrous sulfate (7H.sub.2 O)                                                                0.98                                                                               0.98  0.98  0.98                                           ascorbic acid                                                                              0.6  0.6   0.6   0.6                                             lactic acid  4.5  4.5   4.5   4.5                                             cationized cellulose.sup.1                                                                 --   0.5   0.5   --                                              cationic surfactant.sup.2                                                                  5.4  1.1   --    --                                              cationic surfactant.sup.3                                                                  2.0  --    --    --                                              nonionic surfactant.sup.4                                                                  --   0.5   0.5   0.5                                             nonionic surfactant.sup.5                                                                  1.0  --    --    --                                              behenyl alcohol                                                                            2.0  --    --    --                                              propylene glycol                                                                           10.0 4.0   4.0   4.0                                             perfume      0.2  0.2   0.2   0.2                                             methylparaben                                                                              0.3  0.3   0.3   0.3                                             xanthan gum  0.3  0.3   0.3   0.3                                             sodium hydroxide                                                                           q.s. q.s.  q.s.  q.s.                                            purified water                                                                             balance                                                                            balance                                                                             balance                                                                             balance                                         pH of composition                                                                          3.8  3.8   3.8   3.8                                             Form of composition                                                                        creamy                                                                             transparent                                                                         transparent                                                                         --                                              Conditioning effect                                                                        ⊚                                                                   ⊚                                                                    ○                                                                            x                                               __________________________________________________________________________     Note: .sup.1 to .sup.5 are as defined above in Table 3.                  

EXAMPLE 9: Hair color tone modifier composition

In this Example, invention products 18 and 19 of the formulationsspecified in the following Table 8 were prepared. The invention product18, wherein a direct dye was directly added to the primary agent, wassuitable for daily use. The invention product 19, wherein a direct dyewas directly added to the secondary agent, was a set lotion having ahair color tone modifying effect. The color tone of the hair could beexcellently modified by using either of these compositions.

The first agents of the invention products 18 and 19 were eachhermetically sealed in an Excel bottle.

                  TABLE 8                                                         ______________________________________                                                           Invention Invention                                        Formulation (% by weight)                                                                        product 18                                                                              product 19                                       ______________________________________                                        Primary agent                                                                 ferrous sulfate (7H.sub.2 O)                                                                      0.98      0.98                                            ascorbic acid      0.6       0.6                                              lactic acid        4.5       4.5                                              silicone*.sup.1    0.5       0.5                                              methylparaben      0.3       0.3                                              cationic surfactant*.sup.2                                                                       2.0       2.0                                              cationic surfactant*.sup.3                                                                       5.5       5.5                                              nonionic surfactant*.sup.4                                                                       1.0       1.0                                              behenyl alcohol    2.0       2.0                                              propylene glycol   10.0      10.0                                             common salt        --        1.0                                              perfume            0.2       0.2                                              xanthan gum        0.4       0.4                                              sodium hydroxide   q.s.      q.s.                                             Dye                                                                           Sienna Brown*.sup.5                                                                               0.015    --                                               Straw Yellow*.sup.5                                                                               0.005    --                                               Madder Red*.sup.5   0.040    --                                               disperse                                                                      Violet*.sup.6       0.010    --                                               HC blue No. 2*.sup.6                                                                              0.010    --                                               water              balance   balance                                          pH                 3.8       3.8                                              Secondary agent                                                               hydrogen peroxide (30%)                                                                          1.8       1.8                                              acetanilide         0.02      0.02                                            oxyquinoline        0.01      0.01                                            styling polymer*.sup.7                                                                           2.0       2.0                                              phosphoric acid    q.s.      q.s.                                             Dye                                                                           Sienna Brown*.sup.5                                                                              -- 0.005                                                   Straw Yellow*.sup.5                                                                              --         0.002                                           Madder Red*.sup.5  --          0.0005                                         water              balance   balance                                          pH                 3.0       3.0                                              ______________________________________                                         Note:                                                                         *.sup.1 KF96 (mfd. by Toray Silicone Co.).                                    *.sup.2 Stearyltrimethylammonium chloride.                                    *.sup.3 The same as the one shown by *.sup.3 in Table 5 (Example 5).          *.sup.4 The same as the one shown by *.sup.4 in Table 5 (Example 5).          *.sup.5 Basic dye (mfd. by William, England).                                 *.sup.6 Nitro dye (described in CTFA Dictionary, U.S.A.).                     *.sup.7 Luviskol K30 (mfd. by BASF).                                     

What is claimed is:
 1. A hair color tone modifier compositioncomprising:(1) a first hair treatment composition comprised of: (a) aferrous salt, and (b) a non-reducing organic chelate-forming compoundhaving the formula (II): ##STR5## wherein R and R may be the same ofdifferent and wherein R represents a hydrogen atom, a straight-chain orbranched alkyl group having one to five carbon atoms or an alkenyl grouphaving one to five carbon atoms, and wherein R represents astraight-chain or branched alkyl group having one to five carbon atomsor an alkenyl group having one to five carbon atoms, n is from 0 to 2and m is from 0 to 6, and wherein when m is 1 to 6, said hydroxyl groupmay be bound at any position on said R; and wherein said non-reducingorganic chelate-forming compound (II) is capable of forming a chelatecompound with a ferrous ion having a pH of from 3 to 6, wherein thestability constant (K₁) between said ferrous ion and said non-reducingorganic chelate-forming compound is lower than 3 and wherein saidferrous salt, which is the chelate compound is highly soluble in water;and (2) a second aqueous composition containing 0.01 to 3% by weight ofhydrogen peroxide having a pH from 3 to 6, wherein a direct dye is addedto either composition (1) or (2).
 2. A hair color tone modifiercomposition comprising:(1) a first hair treatment composition as claimedin claim 6; and (2) a second aqueous composition containing 0.01 to 3%by weight of hydrogen peroxide having a pH of from 3 to 6, and wherein0.0001 to 5.0% of a direct dye is added to either composition (1) or(2).
 3. A method for bleaching hair which comprises the sequential stepsof:(a) applying to the hair a hair treatment composition as claimed inclaim 5; and (b) applying to the hair at pH 3 to 6 and aqueouscomposition containing 0.01 to 3% by weight of hydrogen peroxide havinga pH of from 3 to
 6. 4. A method for bleaching hair which comprises thesequential steps of:(a) applying to the hair a hair treatmentcomposition as claimed in claim 6 as the primary agent; and (b) applyingto the hair at pH 3 to 6 an aqueous composition containing 0.01 to 3% byweight of hydrogen peroxide having a pH of from 3 to 6.